THEO

CHEM
ELSEVIER Journal of Molecular Structure (Theochem) 417 (1997) 247-254

A density functional theory study on stability of carbonylmetallate

monoanions Mn(CO)& HFe(CO)i and Co(CO),
Zhida Chen*, Yuqing Deng, Lemin Ll, Guangxian Xu
Drpcumrrrt of Chemistry, State Key f.ahorato~ ofRare Earth Materials Chmictyv andApp/in~tion. Prkin,? lJniw,:\i~, Be(jirl,y 100871. Chino

Received 6 January 1997: accepted 6 January 1997

Abstract

Calculations on optimized geometries, atomic net charges and interatomic Mulliken populations as well as relaxation
energies for the carbonylmetallate monoanions Mn(CO);, HFe(C0); and Co(C0); have been carried out by density functional
theory at the local density approximation (LDA) level and at the LDAINL level with further non-local corrections for exchange
and correlation included self-consistently. On comparison with the corresponding hydrides, there were found to be shorter M-C
distances and longer C-O separations in the carbonylmetallate anions. From Mulliken population analysis, it is shown that H+
dissociation from hydride molecules leads the electronic charges on the carbonylmetallate anions to delocalize further on the
carbonyl groups, while the M-C bonding is strengthened and the C-O bonding is weakened. The relaxation energies calculated
are found to be - 63.01, - 82.00 and - 53.54 kJ mol-’ for Mn(CO);, HFe(C0); and Co(CO);, respectively. 8 1997 Elsevicr
Science B.V.

Kexxwrds: Density functional theory; Stability; Carbonylmetallate monoions; Molecular fragment

1. Introduction supposed to be composed of molecular fragments,

sometimes with some bridging ligands. In fact, the
A number of carbonylmetallate anionic species, carbonylmetallates have been demonstrated to be
M(CO),- (where M is a transition metal and quite useful molecular fragment reagents in molecular
.r=3- -6. := 1 - -4), have been synthesized and syntheses designed for transition metal carbonyl
characterized structurally. Thus, the chemistry of the cluster compounds. It should be pointed out that
carbonylmetallate anions and their derivatives with these carbonylmetallate anions contain the transition
transition metals in low formal oxidation states has metals in low formal oxidation states. even in their
been studied extensively over the past decades [ 1,2]. lowest known oxidation states. The latter species have
With molecular fragment reagents as starting often been referred to as superreduced species. Thus,
materials, molecular syntheses designed for inorganic the study of the electronic structures of carbonyl-
materials and cluster compounds have recently been metallate monoanions has been a subject attracting
carried out in our laboratory on the basis of molecular intense attention [4]. In this paper, we are interested
fragment chemistry [3]. in which a molecule is in using molecular orbital calculations as a practical
guide for laboratory studies and shall put emphasis
* Corresponding author upon bonding energies and the delocalization ot

0166-12X0/97/$17.00 Q 1997 Elsevier Science B.V. All rights reserved

P/I SOl66-1280(97)00016-X
248 2. Chen et d/Journal of Molecular Structure (Theochem) 417 (1997) 247-254

negative charges on these highly reduced transition molecular density and to represent Coulomb and
metal centers for the carbonylmetallate monoanions exchange potentials accurately [ 1 I]. All the calcula-
Mn(CO);, HFe(CO)i and Co(CO),. tions are carried out with a spin-restricted scheme.
Theoretical methods in quantum chemistry may, in The geometry optimization procedure is based on
principle, be applied in organometallic thermo- the analytic gradient method implemented at the
chemistry. However, calculations on large organo- LDA level by Versluis et al. and at the LDA/NL
metallic molecules with the ab initio method are still level by Fan et al. [12]. The optimization uses the
impractical. Thus, much attention has recently been Newton-Raphson method and Hessian is updated
paid to methods based on density functional theory as with the Broyden-Fletcher-Goldfarb-Shanno
an alternative to the ab initio scheme. The application strategy [ 131. Convergence is achieved once changes
of approximate density functional theory to organo- in coordinate values are less than 0.01 unit (distances
metallic chemistry has recently been reviewed by are given in atomic units and angles in radians) and
Ziegler and co-workers [5]. We shall, in the present the norm of all gradient vectors is smaller than 0.01.
investigation, make use of approximate density We have fully optimized the geometries of
functional theory with non-local correction terms of Mn(CO);, HFe(C0); and Co(CO), by LDA and
electron exchange and correlation energies for geo- LDA/NL. The geometry of Mn(C0); has been
metry optimizations, bonding energy calculations optimized respectively within the CA,,, Cjv and D1,
and electronic structures for Mn(CO);, HFe(C0); symmetry constraints. The geometry optimization of
and Co(C0);. HFe(CO)i is within the Cjv symmetry constraint. The
geometry of CO(CO), has been optimized respect-
ively within the Cjy and Td symmetry constraints.
2. Computational details For a comparison of the differences in electronic
structure between Mn(C0); and HMn(CO)s, HFe
All reported calculations are carried out by utilizing (CO), and H2Fe(C0)4, and Co(CO)i and
the Amsterdam density functional (ADF) package, HCO(CO)~, the hydrides HMn(CO)S, H2Fe(CO)_,
version 1.1.3. The local density approximation and HCo(CO)d are also calculated by density func-
(LDA) with local exchange and correlation potentials tional theory with the LDA and LDA/NL approxima-
makes use of the parametrization of Vosko et al. [6]. tions. Structure parameters of these hydrides in our
Non-local corrections (NL) with Becke’s non-local calculations are taken from experimental data
exchange correction [7] and Perdew’s non-local obtained by gas-phase electron diffraction [ 131. In
correlation correction [8] are added in each SCF- our work, the calculated relaxation energies [5]a for
consistent cycle. Convergence is achieved once the Mn(CO);, HFe(C0); and Co(CO), represent the
maximum number of elements of the commutator of energies gained when the Mn(CO);, HFe(C0); and
both the Fock matrix and the density matrix is smaller Co(CO), anions rearrange from the geometries
than lo-’ and the norm of the commutator is under taken up in their hydrides HMn(CO)s, H2Fe(CO)$
lo4 in absolute value. The numerical integration pro- and HCo(CO)+
cedure applied for the calculations is the polyhedron
method developed by Velde and co-workers [9]. The
electronic configurations of the molecular systems are 3. Results and discussion
described by an uncontracted triple-c ST0 basis set
[lo] on Mn 3d,4s, Fe 3d,4s, and Co 3d,4s as well as a 3.1. Optimized structures
double-r ST0 basis set on 0 2s,2p, C 2s,2p, and H 1s.
The 0, C and H atoms are given an extra polarization 3.1.1. Mrl(CO)~
function: 0 3d ({3d =2.00); C 3d ({3d =2.20); H 2p The optimized structures of Mn(C0); under the
({+ = 1.25). The inner core shells for all atoms except Cd,,, Cl” and Djh symmetry constraints are presented
the H atom are treated by the frozen core approxima- in Table 1. The crystal structure data from X-ray
tion. A set of auxiliary s, p, d, f and g ST0 functions, analysis are available for the trigonal-bipyramidal
centered on all nuclei, is introduced to fit the Mn(C0); in ]Ni( 1, lo-phen) 31[Mn(CO)tI 2 (see
 Z. Chrn et al.Nournal of Molecular Structure (Throchern) 417 (1997) 247-254 219

Table I
Optimized geometries”

Symmetry Method M-C,, M-C,, G-O,, C,,,-0,X M-H C,i,-M-C;q O,,-C,,-Mh

LDA I .7x’) I.742 I.165 I.155 101.7 178.5

LDA/NL 1.837 I .794 1.174 I.176 102.3 177. I8
LDA I .77 I I .803 I I67 I.163 Yl.5 177.6
1.786 I.164
LDA/NL 1.825 1.847 1.175 I.169 91.3 177.7
I.832 I.170
LDA 1.771 1.795 I.167 I.163 90.0 180.0
LDAML I .824 1.839 1.177 I.172 90.0 180.0
exptl’ I.798 I.820 I.155 I.153 90.0 17x.2

LDA/NLd I.855 I.854 I.155 I.155 I .589 91.8 I X0.0

Exptl’ 1.856 1.854 1.142’ 1.142’ I.576 94.53 I ‘Xl.I

LDA 1.738 1.748 I.166 I.165 I.518 9Y.5 173.3

LDAPJL I.738 1.797 1.176 I.173 1.533 9Y.S 177.5
Exptl” I .75 1.72 1.15 1.18 I .57 YY.07 Ill.2

Exptl’ 1.802 I .832 1.145’ I.145 I.556 96.Oh 16.5’

148.5’ 176.2’

LDA I.737 I .730 1.167 I.166 _ 107.8 177.2

LDA/NL I.791 I.784 I.174 I.173 108.4 178.0
LDA I .736 I .736 I.164 lOY.5 180.0
LDA/NL I .789 1.789 I.174 109.5 I80.0
Exptl’ I .825( I .76) 1.23(1.17) _ lOY.S(l I?) 167.5(155)
(1.89) ( I .29) (107) (IX())

HCo(CO),
c-3, LDA/NL” I.801 1.803 I.151 I.148 I .499 98.2 179.9
Exptl’ I.818 I .764 I.141 I.141 I.556 99.7 172.6
- _
’ Key: eq. equatorial: ax, axial. Interatomic distances are given in AngstrGm\.
h Bond angles are given in degrees.
’ Ref. [15].
’ Ref. [S]a.
’ Ret’. 1141.
’ Average value.
p Ref. [ Ih].
h C,,-Fe-C,,.
’ Fe+C,,AO,,.
C,,--Fe-C .I\,
’ Fe-C,,PC,i,.
‘Ref [ 171.
250 2. Chen et ai./Journal of Molecular Structure (Theochem) 417 (1997) 247-254

Table 1). For the purpose of comparison, both the within 0.02 A from the crystal structure data [16]
molecular structure for HMn(CO)S obtained by gas- obtained from X-ray diffraction analysis, except Fe-
phase electron diffraction [14] and the calculated C,, which has a deviation of 0.07 A and Fe-H with a
geometry [5]a of this molecule obtained by DFT at deviation of 0.04 A. We are not able to rationalize the
the LDA/NL level are listed in Table 1. It is found in large deviations between experiment and theory for
Table 1 that the geometries optimized by LDA/NL, in this Fe-C,, distance. For the Fe-H distance, we
general, agree better with experimental structures than expect that at least some of the deviation might be
those optimized by LDA, which is consistent with due to experimental uncertainties in the position of
Ziegler’s calculations [5]a. Thus, in this text we the H atom. On the other hand, the calculated bond
shall mainly discuss the results calculated by LDA/ angles are within 0.5” from experimental observations
NL. Our calculations show that for the structures of and reproduce well the experimental fact that the
Mn(C0); under the Cd”, CjV and Djh symmetries, the equatorial CO groups are slightly leaning toward the
Djh geometric configuration is the most stable one in axial hydrogen atom [ 151. Again, it is interesting to
terms of energy. The calculated total bonding energies note the differences in the corresponding bond distances
are found to be 12.63 kJ mol-’ and 4.19 kJ mol-’ between H2Fe(CO)1 and HFe(CO)i. It is found in
lower than those for the Cd, and CjV geometries, Table 1 that the Fe-C,, and Fe-C, experimental
respectively. The calculated geometry is in distances are shortened from 1.802 A and 1.832 A
good agreement with the experimental data [ 151 in H11Fe(C0)4 to 1.75 A and 1.72 A in HFe(CO);,
obtained from X-ray diffraction analysis for the respectively, while the C,,-O,, and C,,-O,, experi-
[Ni(l,lO-ghen)j][Mn(CO)s]~ crystal, with deviations mental separations are lengthened from 1.145 A in
of 0.02 A (bond distance) and 2” (bond angle). It H*Fe(CO)., to 1.15 A and 1.18 A in HFe(CO)i,
should be remembered that our calculations have respectively. These changes in the bond distances
ignored the role of the counterion [Ni( l,lO-phen)]” indicate the effect of the dissociation of H+ ions on
in the crystal field. On the other hand, the calculated the Fe-C and C-O chemical bonds.
Mn-C,, distance of 1.839 .$ is slightly longer than the
Mn-C,, distance (1.824 A), which correctly repro- 3.1.3. Co(CO),
duces the experimental measurements [ 141. Hence We have fully optimized two geometries of
the calculated geometry for Mn(C0); using DFT- Co(CO), with C3” and Td symmetries. The calculated
LDA/NL is satisfactory in our studies. CjV configuration is 0.87 kJ mall’ higher in energy
It is worth pointing out that there is one notable than the Td structure. This agrees well with the experi-
difference in the corresponding Mn-C and C-O mental Td geometry obtained by X-ray analysis of the
distances between HMn(CO)s and Mn(C0);. It is crystal structure for TICO(CO)~ [17]. It should be
shown from the experimental data in Table 1 that pointed out that there are no discrete T~CO(CO)~
after the dissociation of H+ ions in HMn(CO)S, the moieties in the solid state. Thus, the counterion Tl’
Mn-C,, and Mn-C,, separations are shorter by in the TlCo(C0)4 crystal affects significantly the bond
0.058 A and 0.034 A, respectively, while, in contrast, distances in Co(C0);. The experimental Td geometry
the C,,-O,, and C,-O,, distances are longer by for Co(CO), is in fact slightly distorted. The three-
0.013 A and 0.011 A, respectively. It is interesting fold-related carbonyl group has a Co-C-O angle of
to remark here that this trend in bond distance changes 155”, not 180”. Therefore, there are two sets of corre-
is important in understanding the stability of the sponding bond distances and bond angles. The experi-
compounds studied. mental structural data for the two sets are given in
parentheses in Table 1. The calculated Co-C distance
3.1.2. HFe(C0): of 1.789 A is found to be 0.036 A shorter than the
The experimental geometry of the HFe(CO)i anion experimental average value of 1.825 A [ 171. Also, the
has been found to be a configuration with CjV theoretical estimate of the C-O distance agrees with
symmetry [ 161. The geometry optimization in our cal- the experimental average data to within 0.056 A.
culations has been carried out within the CjV sym- However these theoretical values are within the
metry constraint. All bond distances are calculated corresponding experimental bond distances of the
 % Chen ct ul./Journul oJMoleculnr Structure (Them-hem) 417 (1097) 247-254 251

two sets mentioned above. In this case, a direct com-
parison of the bond distances calculated by LDA/NL
between HCO(CO)~ and Co(CO), might help to
understand the change in chemical bonding due to
the H’ dissociation in HCo(CO)+
It is found in Table 1 that the calculated Co-C
distance in Co(C0); is 0.013 i shorter than the
average calculated value of Co-C in HCo(CO)+ In
contrast, the C-O separation in Co(CO), is calculated
to be larger than the average calculated distance of C-
O in HCo(CO)+ It should be noted that the trend in the
decrease of the M-C (where M is Mn, Fe, Co) dis-
tances upon an increase in the C-O separation
becomes obvious. These structural changes show
that when H+ ions in Mn(CO);, HFe(CO)4 and
Co(CO)i are removed by dissociation, the interaction
between the central metal atom and the coordinating
carbon atom at the carbonyl groups becomes stronger
with a concomitant weakening of the bonding
between the carbon and oxygen atoms in the carbonyl
groups.
3.2. Mulliken population analysis
3.2.1. Atomic net churges
For the Mn(CO);, HFe(C0); and Co(W), species
as well as their hydrides, the central transition metal
atom is in a low formal oxidation state. Hence, the
problem of electronic charge distribution in the mole-
cules or anions has been a subject of intense interest.
On the basis of Mulliken population analysis, atomic
net charges for the species mentioned above are given
in Table 2. It is found in Table 2 that the calculated
atomic net charges on the central metal atoms and the
carbon atoms of the carbonyl groups are all positive,
but not too high, while all the oxygen atoms of the
carbonyl groups have negative net charges. To avoid
confusion in the charge signs. we prefer herein to
discuss electronic charges on atoms rather than “net
charges”. It is interesting to note that the electronic
charges on the central metal atoms in the hydride
molecules are greater than those in the corresponding
anions. The dissociation of H- ions in the hydride

Table 2
Atotmc net charges

Symmetry Method M C,, C,, a, O,k H C -0”

LDA 0.4384 0.2383 0.2703 -0.5405 -0.5361 _ -0.2840

LDA/NL 0.45 IS 0.2534 0.2835 -0.557 I -0.ss37 -0.2X69

I,DA -0.0464 0.4294 0.4332 -0.4500 -0.464 I 0.1597 -0.025x

LDA/NL 0.1764 0.4092 0.4095 -0.464 I -0.4778 0.1 I I5 -0.06I6

LDA 0.I8-u 0.2416 0.2675 -0.547 I 4.5523 0.0136 -0.2 187

LDA/NL 0.2380 0.2578 0.2772 -0.5648 -0.5670 -0.027 I -0.29x4

LDA -0.1380 0.4235 0.4382 -0.4503 -0.4448 0.1023 -0.0 I67

LDA/NL 0.063 I 0.406 I 0.4240 -0.4640 -0.4581 0.0606 -0.0460

LDA 0.082 I 0.2787 0.2787 0.5492 4.5492 _ -0.270s

LDA/NL 0.1209 0.2853 0.2853 0.5655 -0.5655 -0.2802

LDA -0.06 I7 0.4298 0.4546 -0.4494 -0.452 I 0. I 182 -0.0086

LDA/NL 0.0893 0.4144 0.4384 -0.4629 -0.4650 0.0829 -0.0376

” Average value.
252 Z. Chen et aL/Journal of Molecular Structure (Themhem) 417 ( 1997) 247-254

molecule will certainly increase the electronic charge
for the anion by one; however, the electronic charge
on the central metal atom in fact does not increase, on
the contrary, it decreases by 0.2751 e, 0.1749 e and
0.0316 e for the Mn, Fe and Co atoms, respectively.
On the other hand, the dissociation of H+ ions in the
hydride molecule leads the electronic charges on the
oxygen and carbon atoms in the carbonyl groups to
increase. Table 2 shows that the electronic charge on
each carbonyl group increases by 0.2253 e, 0.2524 e
and 0.2426 e on average for Mn(Co);, HFe(C0)4 and
Co(CO),, respectively. It is obvious that the electronic
charges for this species of carbonylmetallate anion are
further delocalized on the coordinating carbonyl
groups after the dissociation of H+ ions in the hydride
molecule.
3.2.2. Interatomic M&liken populations
The calculated interatomic Mulliken populations
are listed in Table 3. On comparison with the hydride
molecules, the Mulliken populations between the
central metal atom M and the carbon atom C (both
C,, and C,,) for the Mn(CO);, HFe(CO)i and
Co(CO), anions increase significantly. In Table 3,
the increment of the Mulliken populations between
Mn-C,, and Mn-C,, are found to be 0.1168 and
0.0800, respectively, and 0.1118 and 0.1360 for Fe-
C,, and Fe-C,,, respectively. In the case of Co(CO),,
the Mulliken population on the average for Co-C,,
and Co-C,, increases by 0.1420. While it is shown
in Table 3 that the Mulliken populations for carbonyl
groups in the carbonylmetallate anions decrease
slightly, for Mn(CO);, HFe(C0)4_ and Co(CO), the
situations differ from each other. The decrease of
the C-O Mulliken population for Mn(C0); is the
smallest, being calculated to be 0.0382 and 0.0002
for C,,-O,, and C,,-O,, respectively. In the case of
HFe(CO)i, the Mulliken populations of C,,-O,, and
C,,-O,, decrease by 0.0398 and 0.0562, respectively.
For Co(CO);, the Mulliken population reductions for
C,,-O,, and C,,-O,, are calculated to be 0.0854 and
0.0936, respectively.
The change in the interatomic Mulliken population
might be rationalized on the basis of chemical valence
theory. It is well known that in transition metal
carbonyl compounds there is both CO - M donation
bonding and M - CO donation back bonding. The
latter is formed from d electrons on the metal atom,
back bonding to a a* molecular orbital of the carbonyl
group. The two types of chemical bonding, CO - M
and M - CO, allow the metal atom to combine with
carbonyl group ligands. Thus, when more valence
electrons transfer from the central metal atom to the
carbonyl groups, the M-CO bond will be strength-
ened, resulting in weakening of the C-O bond of
the carbonyl group. Therefore, the carbonyl groups
play an important role in stabilizing carbonylmetallate
anions.
3.3. Relaxation energy
Recently Folga and Ziegler [5]a have investigated
metal-carbon and metal-hydrogen bond energies for
certain metal carbonyl compounds by DFT-LDA!NL.

Table 3
Interatomic Mulliken populations

Species Symmetry Method M-C,, M-C,, c,,-o,, C&J,, M-H

MWO); Dlh LDA 0.2070 0.2548 0.8510 0.8802

LDA/NL 0.3108 0.3326 0.7814 0.8054 _
HMnKO)s C4” LDA 0.2352 0.2892 0.8696 0.8540 0.4426
LDA/NL 0.1940 0.2526 0.8196 0.8056 0.4436
HFe(C0); Ci, LDA 0.3240 0.3674 0.8424 0.8554 0.4104
LDA/NL 0.3952 0.4346 0.7728 0.7760 0.2028
HzFe(C0J4 CZ,, LDA 0.3236 0.3382 0.8628 0.8806 0.3930
LDA/NL 0.2834 0.2986 0.8 I26 0.8322 0.3912
co(c0); Td LDA 0.5328 0.5328 0.8 130 0.8130
LDAA’L 0.5696 0.5696 0.7350 0.7350 _
HCo(CO), C?, LDA 0.4458 0.4668 0.8640 0.8730 0.4408
LDAJTiL 0.4192 0.4360 0.8204 0.8286 0.4344
 Z. Chrn rt ul./Journal of Molrcular Structure (Throchem) 417 I 1097) 247-254 15.7

Table 4 shorter M-C distances and longer C-O separations

Relaxation energies” are found in the carbonylmetallate anions. From
Method HFe(C0); Co(CO)i
chemical bonding theory, Ht ion dissociation leads
Mn(C0);
electronic charges in the anion to further delocalize
LDA -77.14 -88.88 -58.55
on carbonyl groups, and the M-C bonds strengthen,
LDA/NL. -63.01 -82.00 -53.54
while the C-O bonding weakens. Our calculated
‘I In kilojoules per mole. results show that the relaxation energy for the anions
in question are within an order of magnitude of a few
The results. calculated with quite a high accuracy,
tens of kilojoules per mole.
have aroused our interest in the calculation of relaxa-
tion energies for the species of carbonylmetallate
anions. The relaxation energies for the species Acknowledgements
Mn(CO)& HFe(CO)i and Co(CO), are referred to as
the amounts of energy released when these anions are This work was supported by the National Natural
reorganized from the geometry taken up by their Science Foundation of China.
hydride species to the geometry having a stable state
of the anions. From the total bonding energies cal-
culated at the DFT-LDA/NL and LDA levels before References
and after relaxation, we obtained relaxation energies
for these anions, which are given in Table 4. The [I] J.E. Ellis. J. Organomet. Chem. X6 ( 1975) I
relaxation energies from the LDA/NL calculations [?I J.E. Ellis. in: F.G.A. Stone, R. West (Eda.) Advancea in
Organometallic Chemistry. Vol. 3 I. Academic, San Diego.
are slightly lower than those obtained by LDA. We
1990, p. I.
shall only discuss here the relaxation energies cal-
[3] G. Xu. Chem. J. Chin. Umv. I (1984) 100. G. Xu, Ahstr. Paper
culated by LDA/NL. It is shown in Table 4 that the of the 23nd Int. Conf. in Coordination Chemistry. CO. USA,
relaxation energies are -63.01 kJ mol-‘, -82.00 kJ 1984. p. 526. Cr. Xu, in: Yaozeng Huang (Ed. ), New Frontiers
molJ’ and -53.54 kJ mol-’ for Mn(CO);, HFe(C0); in Organometullic and Inorganic Chemistry. Science Press,
Beijmp, China. 1984, p. 73.
and Co(C0):. respectively. The percentage of the
[4] D.A. Penaak, R.J. Mckinney. Inorg. Chem. I8 c1979) 3407.
total bonding energy for the anions in the stable
[S] (a) E. Folga, T. Ziegler. J. Am. Chem. Sot. I I5 (1993) 5169.
state is a small value (0.68% for Mn (CO);, 1.02% (h) T. Ziegler. V. Tschinke, ACS Symp. Ser. 42X. American
for HFe(CO)J and 0.70% for Co(CO),). The relaxa- Chemical Society, Washington DC. 1990. p. 277. (c)
tion energies for the (CO)5Mn. and (CO)&o. radicals T. Ziegler. J.G. Snijders. E.J. Baerends. ACS Symp. Ser.
3X3. American Chemical Society. Washington DC. 1%‘).
are calculated to be -36.13 kJ mol-’ and -1.86 kJ
p, 322. (d) T. Ziegler, V. Tachinke. L. Verslul‘;, NATO AS1
molJ’ at the DFT-LDA/NL level by Folga and Ziegler Ser. C 176, 1986, p. 189. (e) T. Ziegler, J. Pure Appl. Chem. 63
[5]a. Our relaxation energy calculated for the ( 1991) X73. (1.)T. Ziegler, NATO AS1 Ser. 067, 1992. p. 357.
Mn(C0); anion is comparable with that for the corre- (g) T. Ziegler, L. Verrluis. Adv. Chem. Ser. 730 (1992) 75.
sponding (CO)sMn. radical. However, the calculated [6] S.H. Vorko, L. Wilk. M. Nusair. Can. J. Phya. 5X t 1980) 1200.
[7] A.D. Beckc. Phy\. Rev. A 38 (1988) 3098.
relaxation energy for Co(C0); is remarkably larger
[8] J.P. Perdew. Phys. Rev. B 33 (1986) 8822.
than that for the (CO)JCo. radical. Thus, it can be [9] (a) P.M. Boerrlgter. G. te Veldt. E.J. Baercnds. Int. J. Quant.
seen that the relaxation energies calculated for the Chem. 33 (1988) X7. (h) G. te Velde, E.J. Haerends. J. Comput.
anions in question are within an order of magnitude Phys. 99 (1992) 84.
of a few tens of kilojoules per mole. [IO] (a) J.G. Snljdcrs, E.J. Baerends. P. Vernoolj<, At. Nucl. Data
Tablcv 26 (19X2) 483. (h) P. VernoolJs, J.G. Snijders, E.J.
Baerends. Slatcr Type Basis Functions for the Whole Periodic
Systems. Internal Report, Free University of Am\terdam. The

4. Conclusions Netherlands, I98 I.

[I I] J. Kri,jn. E.J. Baerends, Fit Functions in the HFS-Method.
Internal Report. Free University of Amsterdam. The Ncther-
In general, the carbonylmetallate anions in question lands. 1981 (in Dutch).
adopt a geometry with higher symmetry. On com- 1121 (a) L. Verslui\. T. Zielgier, J. Chem. Phys. XX (1988) 322. tb)
parison with the corresponding hydride molecules, L. Fan. T. Zielgcr, J. Chem. Fhya. 95 ( I99 I ) 740 I.
254 Z. Chen et al./Journal of Molecular Structure (Theochem) 417 (I 997) 247-254

[13] (a) H.B. Schlegel, in: K.P. Lawley (Ed.) Ab Initio Methods in
Quantum Chemistry, Adv. Chem. Phys. Vol. 67, Wiley New
York, 1987. (b) J.D. Head, M.C. Zemer, Adv. Quantum Chem.
20 (1988) 1.
(141 E.A. McNeil, F.R. Scholer, J. Am. Chem. Sot. 99 (1977) 6243.
[15] B.A. Frenz, J.A. Ibers, Inorg. Chem. 11 (1972) 1109.
[16] M.B. Smith, R. Bau, .I. Am. Chem. Sot. 95 (1973) 3288.
[ 171 D.P. Schussler, W.R. Robinson, W.F. Edgell, Inorg. Chem. 13
(1974) 1.53.